Diarylamino-trianthrimides



' it hasbeen difilcult to find dyes which dye in desirable gray shades except those which are pro- ?atented Mar. 27, 1945 UNITED-STATES PATENT. OFFICE nmnYmMrNo-rn Edwin C. Buxbaum, Media, Pa., assignor to E. I.- du Pont de Nemours & Company, Wilmington,

Del.,- a corporation of Delaware 9 No Drawing. Original application September 24,

1940, Serial No. 358,099. Divided and this application June 25. 1943, Serial No. 492,305

4 Claims.

inis invention relates to the preparation of new dyestuffs or the anthraquinone series and 1 more particularly to the preparation of new dyestuffs which dye wool and related fibers directly employed in the dyeing of wool and related fibers are simple anthraquinone compounds, 1. e., compounds where only a single anthraquinone nucleus appears in the molecule. Several dianthraquinonylam-ino compounds have been suggested for, useon wool, but with few exceptions such dyes heretofore proposed from this class show poor tinctorial strength, light fastness properties or undesirable changes on chroming. Because of I the poor dyeing properties generally exhibited by the compounds of the dianthrimide series heretofore considered for dyeing wool, it has been assumed that the higher molecular weight trianthrimides would be of no value for this purpos this assumption being supported by the fact that the "straight trianthrimide such as that disclosed in U. S. Patent 863,397 when sulfonated is oi,no practical value as a wool dyestufi.

In'the anthraquinone acid wool dyestufl' field duced by the chroming of dyes which dye directly inother shades. While there are of course a few dyes of the 'anthraquinone series which dye wool and related fibers directly from an acid or neutral bath in gray shades as stated above, in general these dyes are not of desirable shade, or they are defective in light-iastness, tinctorial properties or show" undesirable changes on chroming where such treatment is required for other purposes. A great deal or research has therefore been expendedin an endeavor to find new dyestufls oi the anthraquinone series which will dye wool in desirable gray shades of good fastness properties. 1

It is therefore an object of the invention toproduce new diarylamino trianthrimides from which new dyes oi the anthraquinone series can "be produced which dye wool and related fibers 5 directly in gray shades and which exhibit good dyeing and fastness properties, and which show relatively little change in shade on chroming.

I have found that contrary to the general be-' lief, very desirable dyestufis i'or wool and related s fibers can be produced in the trianthrimide (dianthraquinonylamino anthraquinone) series from trianthrimides which carry one or more arylamino groups of the benzene or naphthalene series directly attached thereto by converting them to water soluble sulionic acids. In the dyes of this series the sulfonation ,takes'plaae readily with sulfuric acid of as low as 93% strength and at temperatures as low as 20 0.. although oleum of as high as may be employed when de- 15 sired. This ease, of sulfonation is apparently due to the presence in the molecule of the aryl amine groups of the benzene or naphthalene series into each of which a sulfonic acid group is readily introduced. In the prior art where sulfonated .fonic acid groups must be introduced into the anthraquinone nucleus which requires more strenuous conditions of suli'onation. These new moles of an amino-arylamino-anthraquinone with one mole oi a dihalogenanthraquinone, the condensation being effected by any of the known processes. employed for the preparation of the a trianthrimide compounds. The invention also contemplates the condensation of two moles of a halogen compound with a diamino diarylamino' anthraquinone such as l,5-diamino-'4,8-dianilino anthraquinone.

All of these compounds dyedirectly in gray shades ranging from greenish-gray, to reddishray and on chroming show only a very small change in shade.

That these new diarylamino t'rianthrimide sul fonic acids, evenewhen they contain no further substituents, should dye in good strength and" show good 'aflinity i'or wool and related fibers is surprising when it is known that the 4,4'-diphenylaminodianthrimide on sulionation has ;very poor amnity and dyeing strength,'for it is generally concluded that the higher molecular weight compounds of the anthraquinone series when sulfonated would have poor amnity for wool and related fibers.

The arylamino groups anthrimide compounds are suggested, the sulcompounds may be prepared by condensing two which may be present in" the molecule may be any of thoseoi' the benzene of 8 hours.

further simple monovalent substltuents such as methyl, amino, nitro, hydroxy and halogen.

These new gray dyestuffs show good light fastness and tinctorial power, and relatively little change in shade on chroming.

The following examples are given to illustrate the invention. The parts used are by weight.

Example 1 A Thirty-one and four-tenths (31.4) parts of additional solvent naphtha and finally with ethyl alcohol and hot water. The base is dried at 100-110 C. It corresponds to the following formula:

. I t i 0 =0 0 Ten parts of the above compound are added to a mixture of 50 parts of sulfuric acid monohydrate and 50 parts of Oleum over a period of one hour. When all of the base has been added, the temperature is raised to 60-'70 0., and held there until sulfonation is complete, which usually takes about thirty minutes. The sulfonated base is then isolated by pouring out into 800 parts of ice and water. filtering, washing acid free with brine and finally drying at 100-110 C. It dyes wool in greenishgray shades which change very little upon chroming and exhibit good light fulling Iastness.

Example 2 quinone in 500 parts of naphthalene in the v presence of 50 parts of potassium acetate and 1 part of copper acetate at 210-215 C. for aperiod When the reaction has been completed, the mass is allowed to cool to 100 C. and diluted with 1000 parts of solvent naphtha. The diluted reaction mass is held two hours additional at 100 C. and then allowed to cool slow y to 50 0., and filtered at this temperature. The filter cake is washed with additional solvent naphtha and finally with hot water and dried.

The compound formed corresponds to the'following formula:

Ten (10) parts of the above base are dissolved in a mixture or 50 parts of sulfuric acid mono-hydrate and 50 parts of 25% oleum. The sulfonation mass is heated to 60 C. for one hour and then poured out into 800 parts of ice and water. It is filtered off, washed acid free with brine and dried. The compound formed dissolves in water with a dark blue color and dyes wool from an acid bath inneutral grayv shades which change very little on chroming. It exhibits good aflinity for the fiber and has desirable fastness properties.

Example 3 Sixteen (16) parts of l-aminoi-anilino-anthraquinone are condensed with 7 parts of 1.B-dichloro-anthraquinone in 250 parts of naphthalene in the presence of 25 parts of potassium acetate and 0.5 part of copper acetate at 2l0-215 C. for a period of six hours.- when the condensation is complete, the mass is cooled responds to the following formula:

l -H U The above compound is easily sulfonated at room temperature by dissolving it in 10% oleum and allowing it'to stir for 8 hours. The isolation of the sulfonated color proceeds in the usual manner. The dyestufl formed dyes wool in greenish-gray shades which change very little on chroming and exhibits excellent fastness to light' Example 4 Thirty-four and three-tenths (343) parts of 1 amino 2 methyl 4 p toluidino-anthraquinone are reacted with 14 parts of 1,5-dichlorovent naphtha and finally washed with alcohol r andfullins.

as'rasis and hot water. The base formed corresponds to the following formula:

' N NO-"om s 0 1 Hi0 N N41 0 Ten' parts of the above base are dissolved in 100 parts 0112.595 oleum and heated to 49 0.;

'until complete sulfonation has occurred. It isthen isolated in the usual manner. The dyestufl dyes wool from an acid bath in taupe shades which become considerably browner on chroming. It exhibits good fastness to light, washing Example 5 Ecanirle 6 lflortv-one (41) parts of l-amino-Z-bromd-- para-toluldino-anthraquinone are reacted with It parts of 1,6-diohloro-anthraquinone in 500 parts of naphthalene in the presence of 50 parts of potassium acetate and one part of copper acetate at 210-215 C. for a period of eight hours. The condensation mass is diluted with sufiicient solvent naphtha to hold the naphthalene in solution and is then cooled to room temperature and filtered. It is washed with additional solvent naphtha, alcohol and hot water. The black powder which is obtained corresponds to the following formula:

Thirty-one and four-tenths (31.4) parts of cooled slowly to room temperature. The diluted,

condensation is filtered, the anthrimide washed with solvent naphtha, alcohol, and finally with water. It corresponds to the following formula:

One hundred .(100) parts of the above compound are dissolved in 1000 parts 'of 12.5% oleum and heated until complete sulfonation is obtained. The acid mass is poured into suflicient ice and water tobring the acid concentration down to 10%. The free disulfonic acid ispreclpitated out and is filteredo6, washed acid free with brine and dried at 100-1l0 C. Itdyes wool from an acid bath in fast gray shades;

Example 7 Twentv-four and three-tenths (24.3) part of l-chloro-anthraquinone are reacted with 21 parts of l,fi-diamino-4,8#dianilino-anthraquinone in 500 parts of naphthalene in the presence of 45 parts of potassium acetate and one part of Loop- Mi l-g E The above compound sulionates easily in strong suliuric acid to give a water soluble dyestufl which dyes wool from an acid bath in blue-gray shades which change slightly on chroming. It exhibits good iastness properties.

If in the above example there is employed l-amlno-li-anilino-anthraquinone in place of lamino-4-anilino-anthraquinone, a much redder shade of gm is produced.

per acetate for eight hours at 210- 215"- C. When the reaction has been completed, the mass is cooled to 140 C. and diluted with 1000 parts of solvent naphtha. then cooled, filtered, washed with alcohol, hot

water-and dried at -1l0 C. It corresponds to the following formula:

' when the above; compound is sulfonated m the usual manner, there is obtained a new gray 76 wool dyestui! which has good tastnes properties.

The diluted condensation is Example "8' If, in the above example, there; is substituted I-amino-4 chloro-anthraquinone in place o! l-chloro-anthraquinone, the following compound is obtained:

Upon sulfonation in the usual manner, this gives a, new blue gray dyestuif' which dyes wool from an acid bath in blue-gray shades which are fast to light and other usual fastness tests.

Example 9 Thirty-one and four-tenths (31.4) parts of 1'-amino-4-anilino-anthraquinone are reacted' with 13.9 parts of 1,4-dichloro-anthraquinone in 450 parts of naphthalene in th presence '01. 45 parts of potassium acetate and one part of copper acetate at 210-215 C. for 8 hours. When the condensation is complete. the massis diluted with solvent naphtha as in the previous examples and filtered. The precipitated trianthrimid'e is washed with additional solvent naphtha, alchol and finally with hot water. It corresponds to the following formula:

Whensulfo'nated' m 10% oleum at SW-65 c. in the usual manner, there is obtained a new wool gray dyestufl. which dyes wool roman acid bath in gray shades of good fastness properties.

The condensation of the amino-arylaminoanthraquinone compounds with the dihalogen anthraquinones may be effected in any one of the numerous media, such as hexalin, ortho-dichloro-benzene, nitro-benzene or other solvents in place of naphthalene used in th examples. If naphthalene is used, any one of numerous solvents can be employed for dilution in place of solvent naphtha, for instance, toluene, benzene 'or--dioxan.: Temperatures ranging from 125- 225 C. may be used depending-on the solvent and length of time condensed.

The sulfonation can be carried out at temperatures ranging from 20 C. to 140 C. Sulfuric acid from 93% strength to 65% oleum can be used. The weaker acids require the higher tem peratures, while the stronger oleums effect sulfonation at lower temperatures.

The advantage of these trianthrimide dyestuffs is that they are fast to light, direct gray dyes which show very little difference either when dyed direct from an acid bath or chromed. In addition, they show good tinctorial power,

The anthn'mide compounds of the types above described are useful not only in the preparation of the sulfonic acid derivatives but may be employed as pigments and as intermediates in the preparation of other colors. v

1; Diarylamino-trianthfimides 'in which each of the amino groups of the trian-thrimide nucleus is connected in an alpha position on at least one anthraquinone molecule, and which trianthrimides carry the arylamino groups in para position on the anthraquinone nucleus-relative to the imino linkages and in which the aryl-groups are monocyclic groups of the benzene series.

2. 4',4"-dianilino-1,5.-(1',1" di anthraquinonylamino) anthraquinone.

3. 4,4"-dianilino-2,6-(1',1" di anthraquinonylamino) anthraquinone.

4. 4,4"-dianilino-1,4-(1',1" anthraquinonlyamino) anthraquinone. l

' EDWIN C. BUXBAUM. 

